CN112601859A

CN112601859A - Method for producing paper or board

Info

Publication number: CN112601859A
Application number: CN201980044039.4A
Authority: CN
Inventors: X.耿; C.Y.钟; J.鲍威尔; P.D.蒙托恩
Original assignee: Corn Products Development Co ltd; Novozymes AS
Current assignee: Corn Products Development Co ltd; Novozymes AS
Priority date: 2018-07-10
Filing date: 2019-07-10
Publication date: 2021-04-02
Also published as: US20210269972A1; EP3821073A1; CA3102221A1; CL2021000014A1; WO2020014351A1; MX2021000113A; BR112021000294A2

Abstract

Disclosed herein is a mixture comprising at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent. The mixture can be used in a process for manufacturing paper or board and in a process for improving the refining performance and/or enhancing the potential of pulp for use in a paper or board mill. In such a method, the mixture is added to a pulp slurry containing cellulosic material during the manufacture of a paper or paperboard product.

Description

Method for producing paper or board

Reference to sequence listing

The present application contains a sequence listing in computer readable form. This computer readable form is incorporated herein by reference.

SEQ ID No. 1 is the Q120H variant of the mature endoglucanase shown in WO 96/29397 as SEQ ID No. 9.

SEQ ID No. 2 is a variant of endoglucanase.

Technical Field

The present invention relates to a method of manufacturing paper or board and a method of improving the refining performance (refinability) and/or enhancing potential of pulp for use in a paper or board mill.

Background

Processes for preparing paper such as printing paper, writing paper, decorative paper, specialty paper or tissue paper and/or board such as kraft board, strong box board, corrugated medium or cardboard by using cellulose pulp are known.

In order to impart the desired papermaking characteristics to the cellulosic fibers, the pulp needs to be subjected to mechanical processing, known as refining. In the refiner, the pulp is subjected to tension, compression and shear during the transfer between the rotating system consisting of the grooved metal plates and the stator. Refining, while effective, consumes a significant portion of the total energy required in the paper and board manufacturing process.

Enzymes are known in the art as a means of altering the refining reaction of cellulosic fibers, thereby reducing manufacturing costs and/or improving certain properties of paper and paperboard. Natural or modified polymers are typically added after or without refining to improve pulp performance (e.g., drainage, dewatering, water retention, etc.) within the papermaking machine-to reduce manufacturing costs-and to provide desired structural and strength characteristics in the finished product.

WO14058557 describes a process for the production of paper or board wherein enzymes and polymers are added to the process. WO17029238 relates to an aqueous surface treatment composition for paper and board comprising degraded starch. WO17034774 describes a method for making paper and paper products wherein a composition comprising laccase, lipase and a cationic fixative polymer is used as an additive to a lignocellulosic suspension.

However, these known processes have had limited effect in reducing manufacturing costs and/or the value imparted to the finished paper and paperboard. Accordingly, there is a need for an improved process for making paper or paperboard.

Disclosure of Invention

In one aspect, the present invention provides mixtures comprising at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent, which mixtures are useful in the manufacture of paper or board and for improving the refining performance and/or enhancing potential of pulp for use in a paper or board mill.

In another aspect, the present invention provides a method of making paper or paperboard comprising the steps of:

a) introducing at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent into the once dried or undried pulp slurry prior to refining to form a treated pulp slurry,

b) refining the treated pulp slurry to form a refined, treated pulp slurry, and

c) the milled, treated pulp slurry is formed into paper or paperboard.

In another aspect, the method of improving the refining performance and/or enhancing the potential of pulp for use in a paper or board mill comprises the steps of: at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent are introduced into the once dried or not dried pulp slurry before or after refining in a paper or board mill.

In yet another aspect, the treated pulp slurry is refined to a target property selected from the group consisting of: a refined, treated pulp slurry reduced freeness (freeness), increased tensile strength of the paper or paperboard product, increased structural properties of the paper or paperboard product, and combinations thereof.

In yet another aspect, the present invention provides a method of making pulp or pulp slurry, the method comprising:

a) introducing into the pulp or pulp slurry, prior to refining, at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent, and

b) the treated pulp or pulp slurry is refined to form a refined, treated pulp or pulp slurry.

In yet another aspect, the present invention provides a method of making pulp or pulp slurry, the method comprising: introducing at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent to the pulp or pulp slurry, either before or after refining, to obtain a refined, treated pulp or pulp slurry.

In one aspect, the mixtures disclosed in the present specification comprise at least one carbohydrate active enzyme and at least one liquid natural polymer and optionally at least one enhancer. In another aspect, the modified liquid natural polymers disclosed in this specification are prepared by: the natural polymer is mixed with at least one carbohydrate active enzyme and optionally at least one enhancing agent. In another aspect, a milled, treated pulp slurry is made by the process of: introducing a mixture comprising at least one carbohydrate active enzyme, at least one liquid natural polymer, and optionally at least one enhancing agent to the pulp slurry prior to refining the once dried or undried pulp slurry, and reacting the mixture with the pulp slurry for a sufficient time to improve at least one characteristic of the pulp slurry for use in making paper or paperboard products. In another aspect, a milled, treated pulp slurry is made by the process of: introducing a mixture comprising at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent to the pulp slurry prior to refining the once dried or undried pulp slurry and allowing the mixture to react with the pulp slurry for a sufficient time such that the pulp slurry has a degree of freedom between 10ml and 890 ml.

Drawings

Figure 1 presents the effect of pretreatment with different dosage levels of LNP and two different carbohydrate active enzymes on tensile strength of handsheets prepared from treated fibers. "EGA" and "EGB" refer to the cellulases of SEQ ID 1 and SEQ ID 2, respectively. Extensions "50" and "100" represent the level of application of 50 grams per ton of dry fiber and 100 grams per ton of dry fiber, respectively.

Figure 2 presents the effect of pretreatment with different dosage levels of LNP and two different carbohydrate active enzymes on the burst strength index of handsheets made from treated fibers. "EGA" and "EGB" refer to the cellulases of SEQ ID 1 and SEQ ID 2, respectively. Extensions "50" and "100" represent the level of application of 50 grams per ton of dry fiber and 100 grams per ton of dry fiber, respectively.

Figure 3 presents the effect of various pretreatments on the tensile strength index of handsheets made from fibers subjected to various degrees of PFI beating.

Fig. 4 presents a comparison between freeness of the pulped pulp made from the pretreated fibers and tensile strength index of the handsheets made from the pretreated and pulped fibers.

Figure 5 presents the effect of pretreatment on the bulk (bulk) of handsheets made from fibers subjected to various degrees of PFI beating.

Figure 6 presents a comparison between tensile strength index and bulk for handsheets made from fibers subjected to various pretreatments and subjected to various degrees of PFI beating.

Figure 7 presents the effect of pretreatment on the tensile index of handsheets prepared from the treated BEKP.

Figure 8 presents the effect of pretreatment on the burst index of handsheets prepared from the treated BEKP.

FIG. 9 presents the effect of pretreatment on the tensile index of handsheets prepared from the treated BEKP and the pulped BSKP at a ratio of 1:1 (w/w).

Definition of

As used herein, the singular forms "a" and "an" include plural referents unless expressly or otherwise indicated by context. For example, "a" natural polymer includes one or more natural polymers, unless indicated otherwise, either explicitly or by context.

In this specification, all stated ranges include all sub-ranges within the stated range.

In the present description and claims, TAPPI refers to the Technical Association of the Pulp and Paper Industry (Technical Association of the Pulp and Paper Industry) which promulgates standards and guidelines for test methods. Such processes are conventionally used in the pulp and paper industry and are available from http:// www.TAPPI.org/Publications-Standards/Standards-Methods.

Pulp is a lignocellulosic fibrous material prepared by chemically or mechanically separating cellulose fibers from wood, fiber crops, or waste paper. Pulp is therefore understood herein as a fluid mixture of fibres and water used for making paper.

Pulp slurry refers to a suspension of fibers in a liquid phase. The slurry may be formed using various suitable liquids (e.g., water) and with any of the components in various ratios, and thus may be described by a range of consistency values (e.g., solids content, water content, etc.) on a weight or volume basis.

In particular referring to the process, the pulp slurry is a suspension of fibers in a liquid phase prior to refining and adding the at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent to the pulp slurry. The addition of the at least one carbohydrate active enzyme, the at least one liquid natural polymer, and optionally the at least one enhancing agent forms a treated pulp slurry, and the refining of the treated pulp slurry forms a refined, treated pulp slurry.

The standard handsheets are handsheets prepared according to TAPPI Standard T205 "to form handsheets for physical testing of pulp (Forming hands for physical tests of pulp)".

Refining is the mechanical treatment of pulp fibers to give them suitable properties for papermaking.

Without being bound by theory or definition, it is believed that refining fibrillates the surface of the fiber and delaminates the fiber walls, thereby affecting the flexibility and conformability of the entire fiber. It is further theorized that the increased flexibility, external fibrillation, and surface area utilize adjacent fibers in the paper and paperboard production process to improve the inter-fiber bonding potential associated with certain optical, structural, and mechanical properties.

Refining may be performed by any suitable process, illustrative processes including, but not limited to, processes that refine pulp slurry between rotating and occasionally static metal elements of, for example, a laboratory beater or an industrial disc or cone refiner.

Freeness is a measure of how quickly water can drain from a sample of dilute fibers. The sample freeness decreases with decreasing drainage rate.

In some embodiments, there is a correlation between freeness values and target levels of pulp refining. In some other embodiments, there is a correlation between the freeness value and the ease of drainage from the wet paper web. In other embodiments, freeness and ease of drainage are primarily highly correlated in the early part of the forming section of the paper machine if freeness is correlated with ease of drainage from the wet paper web.

Freeness can be measured by any standard method. One illustrative test for measuring freeness is based on gravity dewatering through a screen. In such methods, the device is designed so that the operator can judge the dehydration rate by observing the volume of liquid collected in the measuring cylinder.

Fines are objects small enough to pass through a conical hole with a maximum diameter of 76 mm. With respect to the disclosed methods and claims, fines include, but are not limited to, small cellulosic materials, parenchyma cells, and other small cells from wood.

A natural polymer is a polymer that occurs in nature and may be, for example, of plant or animal origin. Examples of suitable natural polymers include, but are not limited to, starch, cellulose, protein, and natural rubber.

Liquid Natural Polymers (LNPs) are natural polymers that have been modified by at least one of chemical (e.g., etherification, acetylation, propylation, phosphatation, ethylation, acidolysis, oxidation, and enzymatic), physical, and/or mechanical transformations to yield natural polymers in liquid form.

Reinforcing agents are natural or synthetic additives used to improve fiber bonding.

Lignocellulosic fibres are fibres from plant dry matter, such as wood, and comprise carbohydrate polymers, such as for example cellulose and hemicellulose, and aromatic polymers, such as for example lignin.

Wet end systems are generally stock preparation and the part of the paper or board machine that comes into contact with the stock of fibers, fillers and/or other additives.

In embodiments, the wet end system includes all unit operations between the brown stock washer to the press section where water is pressed from the wet fibrous web, and any combination of sub-units therein.

The dry end system is the portion of the papermaking system after the wet press section (i.e., the roll press dryer section).

Runnability describes the efficiency with which a stock comprising a pulp of papermaking fibres and various additives is consolidated into a fibrous web by dewatering on an element of a paper or board machine. Several pulp properties can affect the runnability of the stock on the machine, including, but not limited to, freeness, for example.

Detailed Description

Disclosed herein are methods of making paper or paperboard and compositions or mixtures useful for improving paper products. Also disclosed herein is a method of improving at least one characteristic of a pulp slurry for use in a paper or paperboard mill. In one aspect, the improved properties relate to improving the refining performance of the pulp slurry and/or the reinforcement potential of the pulp slurry and/or the runnability of the pulp slurry and/or at least one structural property of the paper and the board, including but not limited to the tensile strength and/or bulk of the paper or the board.

The inventors have surprisingly found that the combination of at least one liquid natural polymer and at least one carbohydrate active enzyme when applied in the pulp slurry prior to refining in a process for making paper or paperboard results in a milled, treated pulp slurry having improved properties including enhanced handsheet, tensile strength at constant or greater bulk, greater freeness, reduced energy required during refining to meet the tensile strength target of the paper or paperboard product, as compared to a refined pulp slurry that has not been treated with the combination of the liquid natural polymer and carbohydrate active enzyme.

As shown in fig. 3, 7, 8 and 9, the combined pretreatment of liquid natural polymer and cellulase surprisingly provides advantages in handsheet enhancement over the control and either component added alone.

Surprisingly, the combined application of liquid natural polymer and cellulase enzyme prior to refining also provided maximum tensile strength while providing greater freeness relative to either the control or either ingredient added alone (see fig. 4).

Cellulases are known to improve the tensile strength of paper or board products, such as for example standard handsheets, often at the expense of bulk. When applied with cellulase, the liquid natural polymer surprisingly reduced bulk loss (see figure 5). In addition, the pretreatment of the blend of liquid natural polymer and cellulase provides higher tensile strength at higher bulk in the resulting handsheets made from the pulped fibers (see fig. 6).

The carbohydrate active enzyme modifies the lignocellulosic fibres in the pulp slurry. In turn, the mixture of the at least one carbohydrate active enzyme, the at least one liquid natural polymer improves the properties of the pulp slurry beyond the case where the enzyme or liquid natural polymer is used alone. Thus, in one aspect, the properties of the pulp slurry are improved after adding at least one carbohydrate active enzyme, at least one liquid natural polymer, and optionally at least one enhancing agent to the pulp slurry prior to refining. In another aspect, the properties of the pulp slurry are improved by adding at least one carbohydrate active enzyme and at least one liquid natural polymer to the pulp slurry prior to refining, and optionally after adding at least one enhancing agent to the pulp slurry after refining. In yet another aspect, the enhancing potential of the pulp slurry is improved after adding at least one carbohydrate active enzyme, at least one liquid natural polymer, and optionally at least one enhancing agent to the pulp slurry prior to refining. In another aspect, the enhancement potential of the pulp slurry is improved by adding at least one carbohydrate active enzyme and at least one liquid natural polymer to the pulp slurry prior to refining, and optionally after adding at least one enhancing agent to the pulp slurry after refining. In yet another aspect, structural properties, such as bulk, of a paper or paperboard product made from a ground pulp, treated pulp slurry treated with at least one carbohydrate active enzyme, at least one liquid natural polymer, and optionally at least one enhancing agent prior to refining are improved. In another aspect, structural properties, such as bulk, of a paper or paperboard product made from a treated milled pulp, treated pulp slurry, by adding at least one carbohydrate active enzyme and at least one liquid natural polymer to the pulp slurry prior to refining, and optionally adding at least one enhancing agent to the pulp slurry after refining, are improved. In yet another aspect, the at least one carbohydrate active enzyme is a cellulase and the at least one liquid natural polymer is derived from starch. This process may also be referred to as a pre-process.

Enzymes suitable for use in the methods described herein are carbohydrate active enzymes, i.e., enzymes that modify, disrupt, or create glycosidic bonds. In one aspect, The carbohydrate active enzyme is from The CAZy database, a database of carbohydrate active enzymes (also known as CAZyme) known to those skilled in The art, and is described, for example, by humped (Lombard) et al in "The carbohydrate-active enzymes database (CAZy) in 2013" (2013 carbohydrate active enzyme database); Nucleic Acids Research [ Nucleic Acids Research ],42(D1): D490-D495. In one aspect, the at least one carbohydrate-active enzyme is a cellulase. In a further aspect, the at least one carbohydrate-active enzyme is an endoglucanase. In yet another aspect, the at least one carbohydrate active enzyme is GH 45. In yet another aspect, the at least one carbohydrate active enzyme has an amino acid sequence that is at least 80%, 85%, 90%, 95%, or 99% identical to SEQ ID No. 1. In a further aspect, the at least one carbohydrate active enzyme has the amino acid sequence of SEQ ID No. 1, or an amino acid sequence with up to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, amino acid changes compared to SEQ ID No. 1. In yet another aspect, the at least one carbohydrate active enzyme has an amino acid sequence that is at least 80%, 85%, 90%, 95%, or 99% identical to SEQ ID No. 2. In a further aspect, the at least one carbohydrate active enzyme has the amino acid sequence of SEQ ID No. 2, or an amino acid sequence with up to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, amino acid changes compared to SEQ ID No. 2.

Liquid natural polymers suitable for use in the methods described herein include natural polymers. Such polymers are natural polymers that have been modified by at least one of chemical (e.g., etherification, acetylation, propylation, phosphatation, ethylation, acidolysis, oxidation, and enzymatic), physical, and/or mechanical transformation means to yield a natural polymer in liquid form. In one aspect, the liquid natural polymer is derived from one or more plant sources. In another aspect, the plant material is starch. In another aspect, the starch may be derived from corn, waxy corn, tapioca, waxy tapioca, wheat, potato, rice and pea (or other legume sources including but not limited to broad beans or lentils), and other high amylose or low amylose variants of plant origin, wherein the low amylose source contains no more than 10% amylose, or less than 5% amylose, or less than 3% amylose, or substantially no amylose (about 0%); and wherein the high amylose source comprises at least 40% amylose, or at least 50% amylose, or at least 60% amylose, or at least 70% amylose, or between about 40% and 80% amylose. In another aspect, the liquid natural polymer is derived from waxy starch. In another aspect, the liquid natural polymer is derived from waxy corn starch.

Reinforcing agents may also be added to the liquid natural polymer. In one aspect, the combination of at least one liquid natural polymer and at least one carbohydrate active enzyme for use in the present invention further comprises at least one enhancer. In another aspect, the reinforcing agents suitable for use in the disclosed methods and claims include, but are not limited to, natural or synthetic additives for improving fiber binding. In another aspect, such additives include, but are not limited to, carboxymethylcellulose (CMC), Glyoxylated Polyacrylamide (GPAM), polyamide-epichlorohydrin (PAE), polyamide polyamine-epichlorohydrin (PAAE), Cationic Polyacrylamide (CPAM), Anionic Polyacrylamide (APAM), amphoteric polyacrylamide, urea-formaldehyde (UF), and melamine-formaldehyde (MF).

In one aspect, the at least one carbohydrate active enzyme is added to the natural polymer during, before or after the conversion of the natural polymer to a liquid natural polymer. In another aspect, the at least one carbohydrate active enzyme is added to the natural polymer after the natural polymer is converted to a liquid natural polymer. Natural polymers, such as starch, may be converted to liquid natural polymers by any suitable process, including but not limited to chemical (e.g., etherification, acetylation, propylation, phosphatation, ethylation, acidolysis, oxidation, enzymatic), physical and/or mechanical conversion to give the natural polymer in liquid form. The manner in which the at least one carbohydrate active enzyme is added to the polymer depends on the liquefaction process, as the enzyme is added at an appropriate time to ensure that the enzyme is still functional in the enzyme/liquid natural polymer mixture. Considerations include, for example, but are not limited to, whether the at least one carbohydrate active enzyme will be able to withstand the pH, temperature, pressure, shear forces, or any combination thereof used in the liquefaction process. In one aspect, the at least one carbohydrate active enzyme is added to the liquid natural polymer after the liquid natural polymer is converted from a natural polymer.

As disclosed herein, the at least one carbohydrate active enzyme, the at least one liquid natural polymer, and optionally the at least one enhancing agent are added to the pulp slurry prior to refining the treated pulp slurry. In another aspect, the at least one carbohydrate active enzyme, the at least one liquid natural polymer, and optionally the at least one enhancing agent are added to the pulp slurry in a pulper of a non-integrated paper mill or a stock tower (stock tower) or equivalent storage vessel of an integrated paper mill.

In one aspect of the method, the pulp slurry is pre-incubated for between 1 minute and 1 hour, or between 10 minutes and 40 minutes or between 15 minutes and 30 minutes before adding the at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent. In another aspect of the method, the at least one carbohydrate active enzyme, the at least one liquid natural polymer, and optionally the at least one enhancing agent may be applied to a pulp slurry and allowed to react with the pulp slurry for a sufficient time to improve at least one characteristic of the pulp slurry used to make paper or paperboard, or the reaction time is between 1 minute and 6 hours, or between 10 minutes and 5 hours, or between 20 minutes and 4 hours, or between 30 minutes and 3 hours, or between 40 minutes and 2 hours, or between 40 minutes and 1 hour, wherein the pulp slurry is optionally preheated to 50-70 ℃, such as to about 60 ℃, prior to adding the at least one carbohydrate active enzyme, the at least one liquid natural polymer, and optionally the at least one enhancing agent. In yet another aspect, the reaction between the mixture of the at least one carbohydrate active enzyme, the at least one liquid natural polymer, and optionally the at least one enhancing agent, and the pulp slurry is stopped by inactivating the enzyme, for example, by adjusting the temperature of the treated pulp slurry or adjusting the pH of the treated pulp slurry. In yet another aspect, the enzymes in the treated slurry are inactivated by the addition of sodium hypochlorite. In yet another aspect of the method, the at least one carbohydrate active enzyme, the at least one liquid natural polymer, and optionally the at least one enhancing agent are applied to the pulp slurry simultaneously or sequentially within 1 second to 6 hours to allow for interaction between the carbohydrate active enzyme(s), the liquid natural polymer(s), and the pulp prior to refining the treated pulp slurry. In another aspect, the at least one enzyme, the at least one liquid natural polymer, and optionally the at least one enhancing agent are added sequentially within 1 hour of each other, such as within 1 second to 5 minutes of each other. In another aspect, the at least one carbohydrate active enzyme, the at least one liquid natural polymer, and optionally the at least one enhancing agent are combined into a mixture and then added together in a common composition to the pulp slurry. In another aspect, the at least one carbohydrate active enzyme, the at least one liquid natural polymer and optionally the at least one enhancing agent may be mixed in a feed line or other feed line feeding the resulting mixture to an introduction port, such as a port on a pulp processing unit or before the suction side of an inter-unit pump. In yet another aspect, the at least one carbohydrate active enzyme, the at least one liquid natural polymer, and optionally at least one enhancing agent are combined into a single suspension prior to addition to the pulp slurry. In another aspect, the at least one carbohydrate active enzyme, the at least one liquid natural polymer, and optionally the at least one enhancing agent are added simultaneously to the pulp from different, separate introduction ports on the same processing unit. In another aspect, the at least one carbohydrate active enzyme, the at least one liquid natural polymer, and optionally the at least one enhancing agent are introduced sequentially as one or more feed streams from the same or different introduction ports or locations on the papermaking system in a short period of time. In aspects using sequential stream feeding, the at least one carbohydrate-active enzyme, the at least one liquid natural polymer, and optionally the at least one enhancer component are added separately in such time that both components are in contact with the pulp in the pulp slurry within a short time, such as within about 5 minutes of each other, or within about 4 minutes of each other, or within about 3 minutes of each other, or within about 2 minutes of each other, or within about 1 minute of each other, or within about 30 seconds of each other, or within a shorter time. In another aspect, after contacting the pulp with the at least one carbohydrate active enzyme, the at least one liquid natural polymer, and optionally the at least one enhancing agent, the resulting treated pulp slurry may be further processed, such as by refining, and used for paper or board formation.

In one aspect, a mixture comprising at least one carbohydrate active enzyme, at least one liquid natural polymer, and optionally at least one enhancing ingredient is added to the pulp slurry at a temperature between about 30 ℃ and about 80 ℃, or between about 40 ℃ and about 70 ℃, or between 50 ℃ and about 60 ℃. In another aspect, a mixture comprising at least one carbohydrate-active enzyme, at least one liquid natural polymer, and optionally at least one enhancing ingredient is added to the pulp slurry at a pH between about 4.0 and about 10, or between about 5.0 and about 9.0, or between about 6.0 and about 8.0. In another aspect, the at least one liquid natural polymer is added to the pulp slurry or to the mixture comprising the at least one carbohydrate-active enzyme and the optional at least one enhancing additive in the following amounts: between 0.01% and 5.0% by weight of the treated pulp, or between 0.05% and 2.0% by weight of the treated pulp, or between 0.10% and 1.0% by weight of the treated pulp, or about 0.5% by weight of the treated pulp. In another aspect, the at least one carbohydrate active enzyme is added to the pulp slurry or to the mixture of the at least one liquid natural polymer and the optional enhancing agent in the following amounts: between 25 and 200g or between 0.005 and 0.1% of dry fibre per metric ton of dry fibre. By definition, the pulp slurry may have various concentrations, but in embodiments, the pulp slurry contains between 1% and 20% fibers, or between 5% and 15% fibers, or about 10% fibers. Further, by definition, pulp slurries may use various suspension liquids, which may vary in pH as described above. In an embodiment, the suspension fluid is deionized water having a pH between 6.0 and 8.0. In an embodiment, the suspension fluid is paper mill process water, such as, for example, fresh water or water recycled from within a paper mill and/or recovered from a water treatment operation, and the pH is between pH 6.0 and 8.0.

In one aspect of the method, the treated pulp slurry is refined to reduce its freeness. In another aspect, the Freeness is between 20ml and 890ml and all subranges therein, as measured by a Freeness determinator (e.g., as can be obtained from TAPPI test method T227 om-99, "pulp Freeness (Canadian standard method)").

In one aspect of the method, the milled, treated pulp slurry increases the tensile strength of the paper or paperboard product. In another aspect, the Tensile strength of the product is between 10Nm/g and 100Nm/g, or between 20Nm/g and 80Nm/g, or between 40 and 70Nm/g, or between about 45Nm/g and 65Nm/g, as measured by a Tensile tester (e.g., as may be obtained from TAPPI T494, "Tensile Properties of Paper and Paperboard (Using a Constant Elongation Apparatus)", and all subranges therein. In another aspect, the tensile strength of the paper or paperboard product varies with the refining level of the treated pulp slurry. In another aspect, the tensile strength is between 10 and 100Nm/g, or between 20 and 80Nm/g, or between 40 and 70Nm/g, or between about 45 and 65Nm/g, in the range of 0 to 1600 revolutions of a PFI refiner. As shown in fig. 3, fig. 7, fig. 8 and fig. 9, the combined pretreatment of the at least one liquid natural polymer and the at least one carbohydrate active enzyme surprisingly provides advantages in handsheet enhancement over control and either component added alone. In another aspect, surprisingly, the combined application of the at least one liquid natural polymer and the at least one carbohydrate active enzyme added to the pulp slurry prior to refining also provides greater tensile strength while providing greater freeness relative to the control or either component added alone, as shown in fig. 4. In another aspect, the tensile strength is between 10Nm/g and 100Nm/g, or between 20Nm/g and 80Nm/g, or between 40 and 70Nm/g, or between about 45Nm/g and 65Nm/g, in the freeness range between 390ml and 490 ml.

In one aspect of the method, the refined, treated pulp slurry increases or maintains bulk of the paper or paperboard product relative to the paper or paperboard product produced after the carbohydrate enzyme treatment alone. In yet another aspect, the paper or paperboard product is a standard handsheet. In another aspect, the bulk is calculated by dividing the thickness of a sheet of paper by its basis weight at 0.1cm³G and 2.0cm³Between/g and all subranges therein. In another aspect, this result is unexpected because cellulases are known to improve the tensile strength of a paper or paperboard product (such as, for example, a standard handsheet) at the expense of bulk. However, cellulose and liquid natural polymers surprisingly reduced the loss of bulk when applied in combination, as shown in figure 5. In embodiments, the bulk of a paper or paperboard product (such as, for example, a standard handsheet) using a treated pulp slurry is within 7.5% of the bulk of the same paper or paperboard product (such as, for example, a standard handsheet) using an untreated pulp slurry at an equivalent refining level, or within 7% of the bulk of the same paper or paperboard product (such as, for example, a standard handsheet) using an untreated pulp slurry at an equivalent refining level, or using an equivalent refining levelWithin 6.5% of the bulk of the same paper or board product (such as e.g. a standard handsheet) of the untreated pulp slurry, or within 6% of the bulk of the same paper or board product (such as e.g. a standard handsheet) using the untreated pulp slurry at an equivalent refining level, or within 5.5% of the bulk of the same paper or board product (such as e.g. a standard handsheet) using the untreated pulp slurry at an equivalent refining level, or within 5% of the bulk of the same paper or board product (such as e.g. a standard handsheet) using the untreated pulp slurry at an equivalent refining level, or between about 7.5% and 0.1% of the bulk of the same paper or board product (such as e.g. a standard handsheet) using the untreated pulp slurry at an equivalent refining level. In another aspect, the pretreatment of the blend of liquid natural polymer and cellulase provides higher tensile strength and higher bulk in the resulting handsheet prepared from the milled, treated pulp slurry, as shown in fig. 6. In an embodiment, the paper or paperboard product will have a thickness of 0.25cm³G and 0.35cm³Between/g or 0.28cm³G and 0.34cm³Between/g or 0.29cm³G and 0.33cm³A bulk between/g, while having a tensile strength between 45Nm/g and 65 Nm/g.

In one aspect of the method, referring to fig. 2 and 8, a paper or paperboard product made using the treated and pulped pulp slurry has a higher burst index at the same refining level. In another aspect, the burst strength index of handsheets made from the milled, treated pulp is between about 3 and about 3.5kPa m²Between/g.

The methods described herein can be practiced in conventional papermaking operations with modifications that can be readily made in accordance with the present disclosure. The method may be practiced, for example, in a wet end operation prior to a refiner as part of a conventional papermaking operation with modifications that may be readily made in accordance with the present disclosure. The method may use many different types of papermaking pulps or combinations thereof. The method may be practiced to make any grade of paper, including, for example, but not limited to, printing and writing paper, medium grade paper, paperboard, linerboard, tissue paper, towel paper, and molded packaging paper.

The present specification further discloses a method of manufacturing pulp or pulp slurry, the method comprising:

The present specification further discloses a method of manufacturing pulp or pulp slurry, the method comprising: introducing at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent to the pulp or pulp slurry, either before or after refining, to obtain a refined, treated pulp or pulp slurry.

The present specification further discloses a mixture comprising a carbohydrate active enzyme, at least one liquid natural polymer and optionally an enhancer. In one aspect, the mixture is prepared by the process of: mixing at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent. In another aspect, the mixture is prepared by an additional process: contacting the at least one carbohydrate-active enzyme with at least one liquid natural polymer.

In one aspect, The carbohydrate active enzyme is from The CAZy database, a database of carbohydrate active enzymes (also known as CAZyme) known to those skilled in The art, and is described, for example, by humped (Lombard) et al in "The carbohydrate-active enzymes database (CAZy) in 2013" (2013 carbohydrate active enzyme database); Nucleic Acids Research [ Nucleic Acids Research ],42(D1): D490-D495. In another aspect, the at least one carbohydrate-active enzyme is a cellulase. In a further aspect, the at least one carbohydrate-active enzyme is an endoglucanase. In yet another aspect, the at least one carbohydrate active enzyme is GH 45. In yet another aspect, the at least one carbohydrate active enzyme has an amino acid sequence that is at least 80%, 85%, 90%, 95%, or 99% identical to SEQ ID No. 1. In a further aspect, the at least one carbohydrate active enzyme has the amino acid sequence of SEQ ID No. 1, or an amino acid sequence with up to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, amino acid changes compared to SEQ ID No. 1. In yet another aspect, the at least one carbohydrate active enzyme has an amino acid sequence that is at least 80%, 85%, 90%, 95%, or 99% identical to SEQ ID No. 2. In a further aspect, the at least one carbohydrate active enzyme has the amino acid sequence of SEQ ID No. 2, or an amino acid sequence with up to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, amino acid changes compared to SEQ ID No. 2.

Suitable liquid natural polymers for use in the mixture include natural polymers. Such polymers are natural polymers that have been modified by at least one of chemical (e.g., etherification, acetylation, propylation, phosphating, ethylation, acidolysis, oxidation, and enzymatic), physical, and/or mechanical transformation to yield a natural polymer in liquid form. In one aspect, the liquid natural polymer is derived from one or more plant sources. In another aspect, the plant material is starch. In another aspect, the starch may be derived from corn, waxy corn, tapioca, waxy tapioca, wheat, potato, rice and pea (or other legume sources including but not limited to broad beans or lentils), and other high amylose or low amylose variants of plant origin, wherein the low amylose source contains no more than 10% amylose, or less than 5% amylose, or less than 3% amylose, or substantially no amylose (about 0%); and wherein the high amylose source comprises at least 40% amylose, or at least 50% amylose, or at least 60% amylose, or at least 70% amylose, or between about 40% and 80% amylose. In another embodiment aspect, the liquid natural polymer is derived from waxy starch. In another embodiment, the liquid natural polymer is derived from waxy corn starch.

In one aspect, reinforcing agents optionally may be used in the mixture including, but not limited to, natural or synthetic additives to improve fiber bonding. In another aspect, such agents include, but are not limited to, carboxymethylcellulose (CMC), Glyoxylated Polyacrylamide (GPAM), polyamide-epichlorohydrin (PAE), polyamide polyamine-epichlorohydrin (PAAE), Cationic Polyacrylamide (CPAM), Anionic Polyacrylamide (APAM), amphoteric polyacrylamide, urea-formaldehyde (UF), and melamine-formaldehyde (MF).

In one aspect, the present specification discloses a treated pulp slurry and a milled, treated pulp slurry. In another aspect, the present specification discloses a treated pulp slurry prepared by the process of: introducing into the pulp slurry, which may or may not have been once dried prior to refining, a mixture comprising at least one carbohydrate active enzyme, at least one liquid natural polymer, and optionally at least one enhancing agent, and reacting the mixture with the pulp slurry for a time sufficient to improve at least one characteristic of the pulp slurry for use in the manufacture of paper. In yet another aspect, the freeness of the milled, treated pulp slurry prepared according to the process described above is between 20ml and 890ml and all subranges therein.

In one aspect, the mixture comprising at least one carbohydrate-active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent is used to prepare a ground, treated pulp slurry for increasing the tensile strength of a paper or paperboard product. In another aspect, the tensile strength index of the product is between 10Nm/g and 100Nm/g, or between 20Nm/g and 80Nm/g, or between 40 and 70Nm/g, or between about 45Nm/g and 65Nm/g, as measured by a tensile tester, and all subranges therein. In another aspect, the tensile strength index of the paper or paperboard product varies with the refining level of the treated pulp slurry. In another aspect, the tensile strength is between 10 and 100Nm/g, or between 20 and 80Nm/g, or between 40 and 70Nm/g, or between about 45 and 65Nm/g, in the range of 0 to 1600 revolutions of a PFI refiner. As shown in fig. 3, 7, 8 and 9, the pretreatment of the pulp slurry with a mixture comprising the at least one carbohydrate active enzyme and the at least one liquid natural polymer surprisingly provides advantages in handsheet enhancement over control and either component added alone. In another aspect, surprisingly, the combined application of the at least one liquid natural polymer and the at least one carbohydrate active enzyme added to the pulp slurry prior to refining also provides greater tensile strength while providing greater freeness relative to the control or either component added alone, as shown in fig. 4. In another aspect, the tensile strength is between 10Nm/g and 100Nm/g, or between 20Nm/g and 80Nm/g, or between 40 and 70Nm/g, or between about 45Nm/g and 65Nm/g, in the freeness range between 390ml and 490 ml.

In one aspect, the use of the mixture comprising at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent increases or maintains the bulk of the paper or paperboard product relative to the paper or paperboard product prepared after carbohydrate enzyme treatment alone. In yet another aspect, the paper or paperboard product is a standard handsheet. In another aspect, the bulk is calculated by dividing the thickness of a sheet of paper by its basis weight. In an embodiment, the bulk of the paper or board product is 0.1cm³G and 2.0cm³Between/g and all subranges therein. In another aspect, this result is unexpected because cellulases are known to improve the tensile strength of a paper or paperboard product at the expense of bulk. However, cellulose and liquid natural polymers surprisingly reduced the loss of bulk when applied in combination, as shown in figure 5. In embodiments, the bulk of a paper or paperboard product (such as, for example, a standard handsheet) using a treated pulp slurry is within 7.5% of the bulk of the same paper or paperboard product (such as, for example, a standard handsheet) using an untreated pulp slurry at equivalent refining levels, or within 7% of the bulk of the same paper or paperboard product (such as, for example, a standard handsheet) using an untreated pulp slurry at equivalent refining levels, or using an untreated paper at equivalent refining levelsWithin 6.5% of the bulk of the same paper or board product of the pulp slurry, such as for example a standard handsheet, or within 6% of the bulk of the same paper or board product using an untreated pulp slurry at an equivalent refining level, such as for example a standard handsheet, or within 5.5% of the bulk of the same paper or board product using an untreated pulp slurry at an equivalent refining level, such as for example a standard handsheet, or within 5% of the bulk of the same paper or board product using an untreated pulp slurry at an equivalent refining level, such as for example a standard handsheet, or between about 7.5% and 0.1% of the bulk of the same paper or board product using an untreated pulp slurry at an equivalent refining level, such as for example a standard handsheet. In another aspect, the pretreatment of the blend of liquid natural polymer and cellulase provides higher tensile strength at higher bulk in the resulting handsheets made from the pulped fibers, as shown in FIG. 6. In an embodiment, the paper or paperboard product (such as, for example, standard handsheets) will have 0.25cm³G and 0.35cm³Between/g or 0.28cm³G and 0.34cm³Between/g or 0.29cm³G and 0.33cm³A bulk between/g, while having a tensile strength between 45Nm/g and 65 Nm/g.

The pulp and pulp slurry used according to aspects of the present disclosure may contain virgin fibers and/or recycled fibers. Any non-wood, softwood or hardwood fibers typically used in the paper industry may be used, including but not limited to bleached or unbleached chemical pulp. Non-limiting examples of fibers include, but are not limited to: bleached Eucalyptus Kraft (BEK) fiber, Bleached Acacia Kraft (BAK) fiber, Bleached Hardwood Kraft (BHK) fiber, unbleached hardwood kraft (UBHK) fiber, Northern Bleached Softwood (NBSK) fiber, Southern Bleached Softwood Kraft (SBSK) fiber, unbleached softwood kraft (UBSK) fiber, Old Corrugated Containers (OCC), Mixed Office Waste (MOW), deinked pulp (DIP), and bleached and unbleached non-wood fiber.

In one aspect, the treated pulp slurry can be used to make paper or paperboard. In another aspect, paper or paperboard made from the treated pulp slurry can be used to make any grade of paper or paperboard. In another aspect, paper made from the treated pulp slurry may be used to make a grade of paper selected from the group consisting of: printing and writing paper, core paper, paperboard, linerboard, tissue paper, towel paper, and molded packaging paper.

Preferred aspects

Preferred aspects of the invention are as follows:

1. a method of making paper or paperboard, the method comprising:

a) introducing at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent into the once dried or undried pulp slurry prior to refining,

b) refining the treated pulp slurry to form a refined, treated pulp slurry, and

c) the milled, treated pulp slurry is formed into paper or paperboard.

2. The method according to aspect 1, wherein the treated pulp slurry is refined to a target property selected from the group consisting of: refining, reduced freeness of the treated pulp slurry, increased tensile strength of the paper or paperboard product, increased structural characteristics of the paper or paperboard product, a reduction in energy required during refining to meet tensile strength targets of the paper or paperboard product, and combinations thereof.

3. The method according to

aspect

1 or 2, wherein the treated pulp slurry is refined to a reduced freeness.

4. The method according to any one of aspects 1-3, wherein the freeness is measured according to Canadian Standard procedure (TAPPI test method T227 om-99) and is between 30ml and 890 ml.

5. The method of any of aspects 1-4, wherein the treated pulp slurry is refined to an increased tensile strength.

6. The method of any of aspects 1-5, wherein the tensile strength is a tensile strength index, measured according to TAPPI test method T220 sp-16, and is between 10Nm/g and 100 Nm/g.

7. The method according to any of aspects 1-6, wherein the treated pulp slurry is refined to achieve increased structural properties of the paper or paperboard product.

8. The method according to any of aspects 1-7, wherein the structural characteristic is the bulk of the paper or paperboard, measured according to TAPPI test method T220 sp-16, and at 0.1cm³G and 2.0cm³Between/g.

9. The method according to any of aspects 1-8, wherein the treated pulp slurry is refined to a target property that is a reduction in energy required during refining to meet a tensile strength target for a paper or paperboard product.

10. The process according to any of aspects 1-9, wherein the at least one carbohydrate active enzyme and the at least one liquid natural polymer are introduced as two separate feed streams.

11. The method according to any of aspects 1-9, wherein the at least one carbohydrate active enzyme and the at least one liquid natural polymer are combined into a suspension prior to introduction into the pulp slurry.

12. The method according to any one of aspects 1-11, wherein the liquid natural polymer is derived from at least one plant source.

13. The method according to any one of aspects 1-12, wherein the plant source is starch, the source of which is selected from the group consisting of: corn, waxy corn, tapioca, waxy tapioca, wheat, potato, rice and/or legumes, and high amylose or low amylose variants thereof.

14. The method of any of aspects 1-13, wherein at least one strengthening agent is introduced to the once dried or undried pulp slurry prior to refining.

15. The method according to any one of aspects 1-14, wherein the at least one enhancer is selected from the group consisting of: carboxymethyl cellulose (CMC), Glyoxylated Polyacrylamide (GPAM), polyamide-epichlorohydrin (PAE), polyamidopolyamine-epichlorohydrin (PAAE), Cationic Polyacrylamide (CPAM), Anionic Polyacrylamide (APAM), amphoteric polyacrylamide, urea-formaldehyde (UF) and Melamine Formaldehyde (MF).

16. The method of any one of aspects 1-15, wherein the liquid natural polymer is derived from waxy starch.

17. The method of any one of aspects 1-16, wherein the liquid natural polymer is derived from waxy corn starch.

18. The method according to any of aspects 1-17, wherein the carbohydrate-active enzyme remains active when the liquid natural polymer is added.

19. The method according to any one of aspects 1-18, wherein the carbohydrate-active enzyme consists of only one component.

20. The method according to any one of aspects 1-19, wherein the carbohydrate-active enzyme is a cellulase.

21. The method according to any of aspects 1-20, wherein the cellulase is an endoglucanase.

22. The method of aspect 21, wherein the endoglucanase is GH 45.

23. The method according to any one of aspects 21-22, wherein the endoglucanase has an amino acid sequence having at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% amino acid sequence identity to SEQ ID No. 1 or SEQ ID No. 2.

24. The method according to any of aspects 21-23, wherein the endoglucanase has the amino acid sequence of SEQ ID No:1 or SEQ ID No:2, wherein up to 10 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) amino acid changes such as substitutions are introduced into the sequence.

25. The method according to aspect 24, wherein the amino acid changes are conservative amino acid substitutions or insertions that do not significantly affect the folding and/or activity of the endoglucanase.

26. The method according to any one of aspects 21-25, wherein the endoglucanase has the amino acid sequence of SEQ ID No:1 or SEQ ID No: 2.

27. The method according to aspect 23, wherein the endoglucanase has an amino acid sequence that has at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% identity to the amino acid sequence of SEQ ID No. 1.

28. The method according to aspect 24, wherein the endoglucanase has the amino acid sequence of SEQ ID No:1, wherein up to 10 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) amino acid changes such as substitutions are introduced into SEQ ID No: 1.

29. The method according to aspect 28, wherein the amino acid changes are conservative amino acid substitutions or insertions that do not significantly affect the folding and/or activity of the endoglucanase.

30. The method according to aspect 26, wherein the endoglucanase has the amino acid sequence of SEQ ID No: 1.

31. The method according to aspect 26, wherein the endoglucanase has the amino acid sequence of SEQ ID No. 2.

32. The method according to aspect 23, wherein the endoglucanase has an amino acid sequence that has at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% identity to the amino acid sequence of SEQ ID No. 2.

33. The method according to aspect 24, wherein the endoglucanase has the amino acid sequence of SEQ ID No. 2, wherein up to 10 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) amino acid changes such as substitutions are introduced into SEQ ID No. 2.

34. The method according to aspect 33, wherein the amino acid changes are conservative amino acid substitutions or insertions that do not significantly affect the folding and/or activity of the endoglucanase.

35. The method according to any of aspects 1-34, wherein the at least one carbohydrate active enzyme and the at least one liquid natural polymer are added to the pulp slurry in a pulper of a non-integrated paper mill or in a stock tower or equivalent storage vessel of an integrated paper mill.

36. The method according to any of aspects 1-35, wherein the pulp slurry is treated with the at least one carbohydrate active enzyme and the at least one liquid natural polymer for a time of up to 6 hours.

37. The method according to any one of aspects 1-36, wherein the at least one carbohydrate active enzyme and the at least one liquid natural polymer are added to the pulp slurry at a temperature of about 30 ℃ to about 80 ℃, about 40 ℃ to 70 ℃, or about 50 ℃ to 60 ℃.

38. The method according to any of aspects 1-37, wherein the at least one carbohydrate active enzyme and the at least one liquid natural polymer are added to the pulp slurry at a pH of about 4.0 to about 10, a pH of about 5.0 to about 9.0, or a pH of about 6.0 to about 8.0.

39. The method according to any one of aspects 1-38, wherein the dosage of the liquid natural polymer is 0.01% to 5.0%, such as about 0.5%, of the total weight of dry solids in the treated pulp.

40. The method according to any of aspects 1-39, wherein the dosage of the liquid natural polymer is 0.05% to 2.0% of the total weight of dry solids in the treated pulp.

41. The method according to any of aspects 1-40, wherein the dosage of the liquid natural polymer is 0.10% to 2.0% of the total weight of dry solids in the treated pulp.

42. The method according to any of aspects 1-41, wherein the dosage of the liquid natural polymer is 0.10% to 1.0% of the total weight of dry solids in the treated pulp.

43. The method according to any one of aspects 1-42, wherein the amount of the at least one carbohydrate active enzyme is from 25g to 200g formulated enzyme product per dry ton of fibre.

44. The method according to any of aspects 1-43, wherein the amount of the at least one carbohydrate active enzyme is 0.005% to 0.1% of dry fiber.

45. The method of any of aspects 1-44, wherein the fiber is a papermaking fiber.

46. The method according to any of aspects 1-45, wherein the fiber is selected from the group consisting of: bleached Eucalyptus Kraft (BEK) fiber, Bleached Acacia Kraft (BAK) fiber, Bleached Hardwood Kraft (BHK) fiber, Unbleached Hardwood Kraft (UHK) fiber, Northern Bleached Softwood Kraft (NBSK) fiber, Southern Bleached Softwood Kraft (SBSK) fiber, unbleached softwood kraft (UBSK) fiber, Old Corrugated Containers (OCC), Mixed Office Waste (MOW), deinked pulp (DIP), and bleached and unbleached non-wood fiber.

47. The method according to any one of aspects 1-46, wherein the fiber is bleached eucalyptus kraft fiber.

48. The method according to any of aspects 1-47, wherein the pulp, paper or paperboard is selected from the group consisting of: printing paper, writing paper, corrugated medium, paperboard, linerboard (kraft and strong), tissue paper, paper towels, cardboard, and molded wrappers.

49. The method of any of aspects 1-48, wherein the method is used in a paper or pulp mill.

50. The method according to any of aspects 1-49, wherein the method is used in a final brown stock washer in a pulp mill, a pulp dryer, a wet stock tower or storage vessel for paper, a unit operation in a board mill, or in between these unit operations.

51. The method of any of aspects 1-49, wherein the method is used in a wet end system in a paper mill.

52. The method according to aspect 51, wherein the method is used to produce a grade of paper selected from the group consisting of: printing and writing paper, core paper, paperboard, boxboard, cardboard, tissue paper, towel paper and molded packaging paper.

53. The method according to any of aspects 1-52, wherein the paper or paperboard product is a standard handsheet.

54. A method of improving at least one property of a pulp slurry for use in a paper or board mill, wherein at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent are introduced into a once dried or never dried pulp slurry prior to refining in the paper or board mill, thereby producing a treated pulp slurry having at least one improved property.

55. The method according to aspect 54, wherein the improved property is one or more properties selected from the group consisting of: the milled pulp, the reduced freeness of the treated pulp slurry, the increased tensile strength of a paper or paperboard product made from the treated pulp slurry, the increased structural properties of a paper or paperboard product made from the treated pulp slurry, the reduction in energy required during refining to meet the tensile strength target of the paper or paperboard product, and combinations thereof.

56. The method according to aspect 54 or 55, wherein the treated pulp slurry is further refined to further reduce the freeness of the treated pulp slurry.

57. The method of any of aspects 54-56, wherein the treated pulp slurry is refined to a reduced freeness.

58. The method according to any one of aspects 54-57, wherein the freeness is measured according to Canadian Standard procedure (TAPPI test method T227 om-99) and is between 30ml and 890 ml.

59. The method according to any of aspects 54-58, wherein the treated pulp slurry is refined to increased tensile strength.

60. The method of any of aspects 54-59, wherein the tensile strength is a tensile strength index, measured according to TAPPI test method T220 sp-16, and is between 10Nm/g and 100 Nm/g.

61. The method of any of aspects 54-60, wherein the treated pulp slurry is refined to achieve increased structural properties of the paper or paperboard product.

62. Root of herbaceous plantThe method of any of aspects 54-61, wherein the structural characteristic is a bulk characteristic calculated according to TAPPI test method T220 sp-16 and is at 0.1cm³G and 2.0cm³Between/g.

63. The method according to any of aspects 54-62, wherein the treated pulp slurry is refined to a target characteristic that is a reduction in energy required during refining to meet a tensile strength target for a paper or paperboard product.

64. The process according to any of aspects 54-63, wherein the at least one carbohydrate active enzyme and the at least one liquid natural polymer are introduced as two separate feed streams.

65. The method according to any of aspects 54-63, wherein the at least one carbohydrate active enzyme and the at least one liquid natural polymer are combined into a suspension prior to introduction into the pulp slurry.

66. The method according to any one of aspects 54-65, wherein the liquid natural polymer is derived from at least one plant source.

67. The method according to any one of aspects 54-66, wherein the plant source is starch, the source of which is selected from the group consisting of: corn, waxy corn, tapioca, waxy tapioca, wheat, potato, rice and/or pea, and high amylose or low amylose variants thereof.

68. The method of any of aspects 54-67, wherein at least one strengthening agent is introduced to the once-dried or undried pulp slurry prior to refining.

69. The method according to any one of aspects 54-68, wherein the at least one enhancer is selected from the group consisting of: carboxymethyl cellulose (CMC), Glyoxylated Polyacrylamide (GPAM), polyamide-epichlorohydrin (PAE), polyamidopolyamine-epichlorohydrin (PAAE), Cationic Polyacrylamide (CPAM), Anionic Polyacrylamide (APAM), amphoteric polyacrylamide, urea-formaldehyde (UF) and Melamine Formaldehyde (MF).

70. The method of any of aspects 54-69, wherein the liquid natural polymer is derived from waxy starch.

71. The method of any of aspects 54-70, wherein the liquid natural polymer is derived from waxy corn starch.

72. The method according to any of aspects 54-71, wherein the carbohydrate-active enzyme remains active when the liquid natural polymer is added.

73. The method according to any one of aspects 54-72, wherein the carbohydrate-active enzyme consists of only one component.

74. The method according to any one of aspects 54-73, wherein the carbohydrate-active enzyme is a cellulase.

75. The method of aspect 74, wherein the cellulase is an endoglucanase.

76. The method of aspect 75, wherein the endoglucanase is GH 45.

77. The method according to any one of aspects 74-75, wherein the endoglucanase has an amino acid sequence that is at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% identical to the amino acid sequence of SEQ ID No. 1 or SEQ ID No. 2.

78. The method according to any of aspects 74-76, wherein the endoglucanase has the amino acid sequence of SEQ ID No:1 or SEQ ID No:2, wherein up to 10 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) amino acid changes such as substitutions are introduced into the sequence.

79. The method according to aspect 78, wherein the amino acid changes are conservative amino acid substitutions or insertions that do not significantly affect the folding and/or activity of the endoglucanase.

80. The method of any one of aspects 74-77, wherein the endoglucanase has the amino acid sequence of SEQ ID No:1 or SEQ ID No: 2.

81. The method according to any one of aspects 74-79, wherein the endoglucanase has an amino acid sequence that is at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% identical to the amino acid sequence of SEQ ID No. 1.

82. The method according to any of aspects 74-79 or 81, wherein the endoglucanase has the amino acid sequence of SEQ ID No:1, wherein up to 10 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) amino acid changes such as substitutions are introduced into SEQ ID No: 1.

83. The method according to aspect 82, wherein the amino acid changes are conservative amino acid substitutions or insertions that do not significantly affect the folding and/or activity of the endoglucanase.

84. The method of any one of aspects 74-77 or 80, wherein the endoglucanase has the amino acid sequence of SEQ ID No: 1.

85. The method according to any one of aspects 74-79, wherein the endoglucanase has an amino acid sequence that is at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% identical to the amino acid sequence of SEQ ID No. 2.

86. The method according to any of aspects 74-79 or 85, wherein the endoglucanase has the amino acid sequence of SEQ ID No:2, wherein up to 10 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) amino acid changes such as substitutions are introduced into SEQ ID No: 2.

87. The method according to aspect 86, wherein the amino acid changes are conservative amino acid substitutions or insertions that do not significantly affect the folding and/or activity of the endoglucanase.

88. The method of any one of aspects 74-77 or 80, wherein the endoglucanase has the amino acid sequence of SEQ ID No: 2.

89. The method of any of aspects 54-88, wherein the at least one carbohydrate active enzyme and the at least one liquid natural polymer are added to the pulp slurry in a pulper of a non-integrated paper mill or in a stock tower or equivalent storage vessel of an integrated paper mill.

90. The method according to any of aspects 54-89, wherein the pulp slurry is treated with the at least one carbohydrate active enzyme and the at least one liquid natural polymer for a time of up to 6 hours.

91. The method according to any one of aspects 54-90, wherein the at least one carbohydrate active enzyme and the at least one liquid natural polymer are added to the pulp slurry at a temperature of about 30 ℃ to about 80 ℃, about 40 ℃ to 70 ℃, or about 50 ℃ to 60 ℃.

92. The method according to any of aspects 54-91, wherein the at least one carbohydrate-active enzyme and the at least one liquid natural polymer are added to the pulp slurry at a pH of about 4.0 to about 10, a pH of about 5.0 to about 9.0, or a pH of about 6.0 to about 8.0.

93. The method according to any of aspects 54-92, wherein the dosage of the liquid natural polymer is 0.01% to 5.0%, such as about 0.5%, of the total weight of dry solids in the treated pulp.

94. The method according to any one of aspects 54-93, wherein the dosage of the liquid natural polymer is 0.05% to 2.0% of the total weight of dry solids in the treated pulp.

95. The method according to any of aspects 54-94, wherein the dosage of the liquid natural polymer is 0.10% to 2.0% of the total weight of dry solids in the treated pulp.

96. The method according to any of aspects 54-95, wherein the dosage of the liquid natural polymer is 0.10% to 1.0% of the total weight of dry solids in the treated pulp.

97. The method according to any one of aspects 54-96, wherein the amount of the at least one carbohydrate active enzyme is from 25g to 200g formulated enzyme product per dry ton of fibre.

98. The method according to any one of aspects 54-97, wherein the amount of the at least one carbohydrate active enzyme is 0.005% to 0.1% of dry fiber.

99. The method of any of aspects 54-98, wherein the fiber is a papermaking fiber.

100. The method according to any of aspects 54-99, wherein the fiber is selected from the group consisting of: bleached Eucalyptus Kraft (BEK) fiber, Bleached Acacia Kraft (BAK) fiber, Bleached Hardwood Kraft (BHK) fiber, Unbleached Hardwood Kraft (UHK) fiber, Northern Bleached Softwood Kraft (NBSK) fiber, Southern Bleached Softwood Kraft (SBSK) fiber, unbleached softwood kraft (UBSK) fiber, Old Corrugated Containers (OCC), Mixed Office Waste (MOW), deinked pulp (DIP), and bleached and unbleached non-wood fiber.

101. The method according to any one of aspects 54-100, wherein the fiber is bleached eucalyptus kraft fiber.

102. The method according to any of aspects 54-101, wherein the pulp, paper or paperboard is selected from the group consisting of: printing paper, writing paper, corrugated medium, linerboard (kraft and strong), tissue paper, towel paper, and cardboard.

103. The method of any of aspects 54-102, wherein the method is used in a paper or pulp mill.

104. The method according to any of the aspects 54-103, wherein the method is used in a final brown stock washer in a pulp mill, a pulp dryer, a wet stock tower or storage vessel for paper, a unit operation in a board mill, or in between these unit operations.

105. The method of any of aspects 54-103, wherein the method is used in a wet end system in a paper mill.

106. The method according to aspect 105, wherein the method is used to produce a grade of paper selected from the group consisting of: printing and writing papers, core papers, linerboards, tissue papers, and toweling papers.

107. A method of making pulp or pulp slurry, the method comprising:

108. A method of manufacturing paper or paperboard or for manufacturing pulp or pulp slurry, the method comprising: introducing at least one carbohydrate active enzyme, at least one liquid natural polymer, and optionally at least one enhancing agent to the pulp or pulp slurry, either before or after refining, to obtain a treated pulp or pulp slurry, thereby forming a refined, treated pulp or pulp slurry.

109. The method of aspect 108, further comprising any one of aspects 1-107.

110. A mixture comprising at least one carbohydrate active enzyme and at least one liquid natural polymer, and optionally an enhancer.

111. A mixture for the manufacture of paper or board comprising at least one carbohydrate active enzyme and at least one liquid natural polymer, and optionally an enhancing agent.

112. The mixture according to aspect 110 or 111, for use in the manufacture of a pulp slurry having a freeness of between 30ml and 890ml, measured according to canadian standard procedure (TAPPI test method T227 om-99).

113. The mixture according to any of aspects 110-112 for use in the manufacture of a paper or paperboard product having a tensile strength of between 10Nm/g and 100Nm/g, measured according to TAPPI test method T220 sp-16.

114. The mixture according to any one of aspects 110-113, for use in the manufacture of a composition having a thickness of 0.1cm³G and 2.0cm³A paper or board product having a bulk of between/g, calculated according to TAPPI test method T220 sp-16.

115. A treated pulp or pulp slurry made by the method of any one of aspects 1-109.

116. A treated pulp or pulp slurry having a freeness of between 30ml and 890ml, measured according to canadian standard procedure (TAPPI test method T227 om-99).

117. A paper or paperboard product made using the treated pulp slurry of aspect 115 or 116, having a tensile strength of between 10Nm/g and 100Nm/g, measured according to TAPPI test method T220 sp-16.

118. A paper or paperboard product made using the treated pulp slurry of any one of aspects 115 and 117, having a thickness of 0.1cm³G and 2.0cm³Bulk between/g, calculated according to TAPPI test method T220 sp-16.

119. The paper or paperboard product of aspect 117 or 118, selected from the group consisting of: printing paper, writing paper, medium grade paper, cardboard, linerboard, tissue paper, towel paper, and molded packaging paper.

The invention is further described by the following examples, which are not intended to be limiting in any way. It will be appreciated by those of ordinary skill in the art that variations may be made in the methods and products disclosed in the examples which will be within the spirit of the invention and the scope of the claims.

Examples of the invention

Example 1-pretreatment of cellulose fibers Using a combination of liquid Natural polymers and enzymes

10 pulp samples, each equivalent to 24 grams of oven dried bleached eucalyptus kraft fiber, were prepared by diluting undried pulp fibers with deionized water to a consistency of 10% (w/w). The resulting pulp slurry (pH 7.8) was then preincubated at 40 ℃ for 20 minutes. After pre-incubation, liquid compositions of liquid natural polymer, LNP derived from waxy maize starch, cellulase A from Novozymes (Bagsvaerd, Denmark) of SEQ ID No:1 and/or cellulase B from Novozymes (Bagsvaerd, Denmark) of SEQ ID No:2 were added to 10 pre-warmed samples according to Table 1.

Table 1:

where applicable, a formulated liquid natural polymer was added to provide 5kg of dry waxy corn starch per metric ton of oven dried bleached eucalyptus kraft fiber. Where applicable, the formulated cellulases of SEQ ID No:1 and SEQ ID No:2 were added to provide 50 or 100g of formulated cellulase per metric ton of oven dried fiber. All pulps were incubated at 40 ℃ and pH 7.8 for 60 minutes in a tank reactor immersed in a water bath. Continuous stirring was performed using an impeller.

After incubation, sodium hypochlorite was added to each pulp fraction to inactivate the enzyme. Note that: all pulps received the same amount of hypochlorite (20ppm active chlorine).

All pulps were diluted to a consistency of 0.3% for freeness determination according to TAPPI standard T227 om-99. Each pulp was used to prepare 1.2g (60 g/m) of six sheets according to TAPPI Standard T205²) And (4) making paper by hand. Physical tests (e.g., tensile strength index and burst strength index) were performed according to the corresponding TAPPI standard procedure.

Results

As shown in fig. 1 and 2, the combined pretreatment of the liquid natural polymer and either cellulase enzyme surprisingly provides advantages in handsheet enhancement over the control and either component added alone.

EXAMPLE 2 Pre-refiner pretreatment of cellulose fibers Using a combination of liquid Natural polymers and enzymes

13 parts pulp slurry was prepared by diluting 24 grams of oven dried equivalent of undried bleached eucalyptus kraft fiber to a consistency of 10% (w/w) with deionized water. The resulting pulp slurry (pH 7.8) was then separately preincubated at 40 ℃ for 20 minutes. After the pre-incubation, the pulp slurry was divided into one group containing 4 parts and three groups each containing 3 parts. The first group contained 4 copies as an untreated control group (labeled "control"). The first group (labeled "LNP") containing 3 portions of slurry was treated with liquefied waxy corn starch (from angulars, Westchester, Illinois). A second group comprising 3 portions of the slurry was treated with cellulase A from Novoxin (Bagsvaerd, Denmark) of SEQ ID No:1 (labeled "cellulase A"). A third group, containing 3 slurries, was treated with both the cellulase a and the liquefied waxy corn starch (labeled "LNP + cellulase a"). In all relevant examples, liquefied waxy corn starch formulated was added to provide 5kg of dry waxy corn starch per metric ton of oven dried bleached eucalyptus kraft fiber. In all relevant examples, the formulated cellulase A of SEQ ID No:1 was added to provide 100g of formulated cellulase per metric ton of oven dried fiber. All pulps were incubated at 40 ℃ and pH 7.8 for 60 minutes in a tank reactor immersed in a water bath. Continuous stirring was performed using an impeller.

The pulp pad was prepared by vacuum filtration. The filtrate is passed back through the pad once to capture small materials (e.g., fines and fines). The filtrate from each pulp was used to dilute the respective pad to a consistency of 10% (w/w). The pulps from the control and each set of pretreatments were beaten at 0, 500 and 1500 revolutions in a standard PFI refiner operating at 0.2mm gap and 1765N/mm bar length load. Subsequently, the pulp was diluted to a consistency of 0.3% for determining freeness according to TAPPI standard T227 om-99. Each slurry was used to prepare 1.2g (60 g/m) of six sheets according to TAPPI Standard T205²) And (4) making paper by hand. Physical tests (e.g., tensile strength index and burst strength index) were performed according to the corresponding TAPPI standard procedure.

Results

As shown in fig. 3, the combined pretreatment of the fibers with liquid natural polymer and cellulase surprisingly provides an advantage in handsheet enhancement over the control and either component added alone.

Cellulases are known to improve the tensile strength of paper or board products (such as e.g. standard handsheets) at the expense of bulk. When applied with cellulase, the liquid natural polymer surprisingly reduced bulk loss (see figure 5). In addition, the pretreatment of the blend of liquid natural polymer and cellulase provides higher tensile strength at higher bulk in the resulting handsheets made from the pulped fibers (see fig. 6).

Example 3-pretreatment of cellulose fibers Using a combination of liquid Natural polymers and enzymes

The once dried Bleached Eucalyptus Kraft Pulp (BEKP) was soaked in deionized water at 10% (w/w) consistency overnight at room temperature and re-pulped at 500rpm for 5 minutes. The resulting pulp was concentrated by centrifuge, dispersed and stored at 4 ℃ until use.

4 pulp samples were prepared by dilution with deionized water to a consistency of 4.0% (w/w) -each pulp sample equates to 24 grams of oven dried fiber. The resulting pulp slurry (pH 6.8) was then preincubated at 40 ℃ for 30 minutes. After pre-incubation, a liquid composition of liquid natural polymer, LNP derived from waxy maize starch, and cellulase A from Novitin (Bagsvaerd, Denmark) of SEQ ID No:1 was added to the preheated pulp slurry according to Table 2.

Table 2:

sample numbering	Identification	LNP(kg/t)	Cellulase A (g/t)
				1	BEKP-ctrl	-	-
2	BEKP-Enz	-	150
				3	BEKP-LNP	7.5	-
4	BEKP-LNP/Enz	7.5	150

Where applicable, a formulated liquid natural polymer was added to provide 7.5kg of starch solids per metric ton of oven dried fiber. Where applicable, the formulated cellulase of SEQ ID No:1 was added to provide 150g of formulated cellulase per metric ton of oven dried fiber. All pulps were incubated at 40 ℃ and pH 6.8 for 30 minutes in a tank reactor immersed in a water bath. Continuous stirring was performed using an impeller.

After incubation, sodium hypochlorite was added to each pulp slurry to inactivate the enzyme. Note that: all pulps received the same amount of hypochlorite (20ppm active chlorine).

All pulps were diluted to 1.2% consistency for disintegration and further diluted to 0.3% consistency for freeness determination according to TAPPI standard T227 om-99. Each pulp was used to prepare 1.2g (60 g/m) of six sheets according to TAPPI Standard T205²) And (4) making paper by hand. Physical tests (e.g., tensile strength index and burst strength index) were performed according to the corresponding TAPPI standard procedure.

Results

As shown in fig. 7 and 8, the combined pretreatment of liquid natural polymer and cellulase surprisingly provides an advantage in handsheet enhancement over either control or added separately.

Example 4-pretreatment of cellulose fibers Using a combination of liquid Natural polymers and enzymes

The once dried Bleached Eucalyptus Kraft Pulp (BEKP) was soaked in deionized water at 10% (w/w) consistency overnight at room temperature and re-pulped at 500rpm for 5 minutes. The resulting pulp was thickened, dispersed and stored at 4 ℃ for later use by a centrifuge.

4 BEKP samples, each equivalent to 24 grams of oven dried fiber, were prepared by dilution to a consistency of 4.0% (w/w) with deionized water. The resulting pulp slurry (pH 6.8) was then preincubated at 40 ℃ for 30 minutes. After pre-incubation, a liquid composition of liquid natural polymer, LNP derived from waxy maize starch, and cellulase A from Novitin (Bagsvaerd, Denmark) of SEQ ID No:1 was added to the preheated pulp slurry according to Table 3.

All BEKP samples were diluted to a consistency of 1.2% (w/w) for disintegration and further diluted to a consistency of 0.3% (w/w) for determination of freeness according to TAPPI standard T227 om-99.

Table 3:

the once dried Bleached Softwood Kraft Pulp (BSKP) was soaked in deionized water at 10% (w/w) consistency overnight at room temperature and repulped at 500rpm for 7 minutes. The resulting pulp was thickened, dispersed and stored at 4 ℃ for later use by a centrifuge.

1 BSKP sample, equivalent to 24 grams of oven dried fiber, was prepared by dilution to a consistency of 4.0% (w/w) with deionized water. The resulting pulp slurry (pH5.4) was adjusted to pH 6.8 by adding about 0.2ml of 1M NaOH solution and then incubated at 40 ℃ for 60 minutes.

After incubation, the BSKP samples were concentrated to a consistency of 10% (w/w) and refined using a PFI refiner according to the conditions listed in table 3.

After refining, the BSKP samples were diluted to a consistency of 1.2% (w/w) for disintegration and further diluted to a consistency of 0.3% (w/w).

Each portion of BEKP (consistency 0.3% (w/w)) was blended with the milled BSKP (consistency 0.3% (w/w)) at a ratio of 1/1(w/w) and used to prepare 1.2g (60 g/m) of six sheets according to TAPPI standard T205²) And (4) making paper by hand. Physical tests (e.g., tensile strength index and burst strength index) were performed according to the corresponding TAPPI standard procedure.

Results

As shown in fig. 9, pretreatment with a combination of liquid natural polymer and cellulase significantly increased tensile strength relative to the control or either component added alone.

Sequence listing

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<120> method for manufacturing paper or paperboard

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Claims

1. A method of making paper or paperboard, the method comprising:

b) refining the treated pulp slurry to form a refined, treated pulp slurry, and

c) the milled, treated pulp slurry is formed into paper or paperboard.

2. The method according to claim 1, wherein the treated pulp slurry is refined to a target property selected from the group consisting of: the ground pulp, the reduced freeness of the treated pulp slurry, the increased tensile strength of the paper or paperboard product, the increased structural characteristics of the paper or paperboard product, the reduction in energy required during refining to meet the tensile strength target of the paper or paperboard product, and combinations thereof.

3. The method according to claim 1 or 2, wherein the treated pulp slurry is refined to a reduced freeness.

4. The method according to claim 2 or 3, wherein the freeness is measured according to Canadian Standard procedure (TAPPI test method T227 om-99) and is between 30ml and 890 ml.

5. The method according to any one of claims 1 to 4, wherein the treated pulp slurry is refined to increased tensile strength.

6. Method according to any one of claims 2 to 5, wherein the tensile strength is a tensile strength index, measured according to TAPPI test method T220 sp-16, and is between 10 and 100 Nm/g.

7. The method according to any one of claims 1 to 6, wherein the treated pulp slurry is refined to achieve increased structural properties of the paper or paperboard product.

8. The method according to any one of claims 2 to 7, wherein the structural characteristic is the bulk of the paper or paperboard, measured according to TAPPI test method T220 sp-16, and at 0.1cm³G and 2.0cm³Between/g.

9. Process according to any one of claims 1 to 8, wherein the at least one carbohydrate active enzyme and the at least one liquid natural polymer are introduced as two separate feed streams.

10. The method according to any of claims 1 to 9, wherein the at least one carbohydrate active enzyme and the at least one liquid natural polymer are combined into a suspension prior to introduction into the pulp slurry.

11. The method according to any one of claims 1 to 10, wherein the carbohydrate-active enzyme is a cellulase.

12. The method according to any one of claims 1 to 11, wherein the method is used in a paper or pulp mill, preferably wherein the method is used in a unit operation of a final brown stock washer, a pulp dryer, a wet stock tower or storage vessel for paper, a board mill, or in between unit operations in a pulp mill.

13. A method of improving at least one property of a pulp slurry for use in a paper or board mill, wherein at least one carbohydrate active enzyme, at least one liquid natural polymer and optionally at least one enhancing agent are introduced into a once dried or never dried pulp slurry prior to refining in the paper or board mill, thereby producing a treated pulp slurry having at least one improved property.

14. The method according to claim 13, wherein the treated pulp slurry is further refined to further reduce the freeness of the treated pulp slurry.

15. The method according to claim 13 or 14, wherein the improved property is one or more properties selected from the group consisting of: the milled pulp, the reduced freeness of the treated pulp slurry, the increased tensile strength of a paper or paperboard product made from the treated pulp slurry, the increased structural properties of a paper or paperboard product made from the treated pulp slurry, the reduction in energy required during refining to meet the tensile strength target of the paper or paperboard product, and combinations thereof.

16. The method according to any one of claims 1 to 15, wherein the pulp, paper or paperboard is selected from the group consisting of: printing paper, writing paper, corrugated medium, linerboard (kraft and strong), tissue paper, towel paper, and cardboard.

17. A method of making pulp or pulp slurry, the method comprising:

18. A method of manufacturing paper or paperboard or for manufacturing pulp or pulp slurry, the method comprising: introducing at least one carbohydrate active enzyme, at least one liquid natural polymer, and optionally at least one enhancing agent to the pulp or pulp slurry, either before or after refining, to obtain a treated pulp or pulp slurry, to form a refined, treated pulp or pulp slurry.

19. A treated pulp or pulp slurry made by the method of any one of claims 1 to 18.

20. The treated pulp or pulp slurry of claim 19, having a freeness of between 30ml and 890ml, measured according to canadian standard procedure (TAPPI test method T227 om-99).

21. A paper or paperboard product made using the treated pulp slurry of any one of claims 1 to 20, having a tensile strength of between 10Nm/g and 100Nm/g as measured by TAPPI test method T220 sp-16.

22. A paper or paperboard product made using the treated pulp slurry of any of claims 1 to 20, having 0.1cm³G and 2.0cm³A bulk between/g, the bulk being according to TAPPI test method T220 sp-16.

23. The paper or paperboard product according to claims 21-22, selected from the group consisting of: printing paper, writing paper, medium grade paper, cardboard, linerboard, tissue paper, towel paper, and molded packaging paper.

24. A mixture comprising at least one carbohydrate active enzyme and at least one liquid natural polymer, and optionally an enhancer.

25. A mixture for the manufacture of paper or board comprising at least one carbohydrate active enzyme and at least one liquid natural polymer, and optionally an enhancing agent.